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Abstract
The crystal structure, crystal chemistry and surface properties of kaolinite in kaolin clays have been studied. The crystallinity
index was lower for hard kaolin than for soft kaolin. The oatability of hard kaolin was lower than that of soft kaolin. Hard kaolin
was the dominant kaolin in bauxite. A new type of collector for hard kaolin was studied in order to selectively separate kaolin from
diaspore in bauxite. The surface zeta potential variation of the hard kaolin as a function of pH was almost the same as that of the
soft kaolin. The IEP of the hard kaolin varied from 2.5 to 3.8. The SiO2 (wt%) content of the several kaolins showed negative
correlations with IEP, but Al2 O3 (wt%) content showed positive correlation with IEP. The crystallinity index of kaolinite was not the
major factor determining IEP. In the broad range of pH, the negative potential of the hard kaolin was lower than that of the soft
kaolin. At the point (pH 7.3) of zero net proton charge at the edge of the kaolinite, TFe (wt%) showed negative correlation with
surface zeta potential of the kaolin, but the crystallinity index of kaolinite showed a positive correlation.
2003 Elsevier Ltd. All rights reserved.
Keywords: Froth otation; Oxide ores; Industrial minerals
1. Introduction
Each kaolinite layer comprises one octahedral sheet
and one tetrahedral sheet. Kaolinite layers are less
tightly bound together in the c direction, by hydrogen
bonding between hydroxyl sites on the gibbsite basal
plane and the oxygens of the silicon tetrahedral sheet.
Kaolinite has dierent surface structures between base
planes and edge planes. (0 0 1) plane is its base plane.
(1 1 0) and (0 1 0) planes are the edge planes. Thus, kaolinite is known to have a heterogeneous surface charge.
The surface electric properties of kaolinites have been
investigated by many authors (Hussain et al., 1996;
Wieland and Stumm, 1992; Herring et al., 1992; Newman, 1987; Rand and Melton, 1977; Schoeld and
Samson, 1954; Williams and Williams, 1978; Brady et al.,
1996; Yuan and Pruett, 1998; Tar et al., 1999; Johnson
et al., 2000). The basal surfaces of kaolinite are believed
to carry a constant structural charge due to the isomorphous substitution of Si4 by Al3 , whereas the
charge on the edges is due to the protonation/deprotonation of exposed hydroxyl groups and depend on the
Corresponding author.
E-mail addresses: hyh@mail.csu.edu.cn (Y. Hu), lxwdr@mail.csu.
edu.cn (X. Liu).
0892-6875/$ - see front matter 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2003.07.006
1280
positive charge in low solution pH (Williams and Williams, 1978; Brady et al., 1996). Clays from ve dierent
commercial deposits in Georgia were studied to understand the variations of zeta potential and related fundamental properties (Yuan and Pruett, 1998). The
results suggest that higher negative zeta potential is related to exchangeable or soluble calcium ions in the
clays. The charge properties of well and poorly ordered
were studied (Tar et al.,
kaolinite and halloysite-7 A
1999). The curves of zeta potential vs. pH showed the
same pH dependency for the three minerals, but a
gradual increase of zeta potential when passing from
through the
well ordered kaolinite to halloysite-7 A
poorly ordered kaolinite.
Zeta potential represents the electric potential at the
shear plane between a particle and the surrounding
liquid when the charged particle moves in an electric
eld (Brady et al., 1996; Wang and Hu, 1988). It is one
of the most important surface properties of minerals
determining the eectiveness of commercial mineral
separation processes such as otation. Although the
oatability of the kaolinite was researched (K
oster et al.,
1992; Choi et al., 1993), the gap in the otation behavior
between hard kaolin and soft kaolin has seldom been
studied. In bauxite otation research, it was found that
the otation behavior between hard kaolin and soft
kaolin was dierent. To understand the mechanism of
kaolin otation, it is imperative to understand how zeta
potential varies in the kaolins. This paper investigates
the eect of the crystal structure, chemical composition and other mineralogical properties of kaolins and
kaolinites on their surface charge properties and the
surface iso-electric points (IEP).
2. Experimental
2.1. Materials
Kaolin clays from four dierent deposits were collected for this study. Sample Ka-ML from Hunan Miluo
was representative of the so-called soft kaolin type.
The other three samples Ka-JX, Ka-DYG, Ka-MC were
from Henan Jiaxian, Henan Dayugou and Henan Mianchi respectively. They were of the hard kaolin type.
The chemicals used in the present study include: acetic
acid (AR), dodecyl amine (AR) and hexadecyl trimethyl
ammonium bromide (AR). HCl and NaOH (AR) were
used for pH adjustment. The high-purity water used in
the experiments was distilled water.
2.2. Methods
A powder diractometer (Shimadzu) was run in the
reection mode with graphite-ltered Cu-Ka radiation
(50 mV, 100 mA), and a goniometer speed of 4 2h/min.
1281
20
-20
-40
2
10
12
pH
Table 2
The iso-electric point (IEP) of the dierent kaolins
Ka-ML
Ka-JX
Ka-MC
Ka-DYG
3.34
3.62
3.78
2.82
Table 1
Crystallinity index of kaolinite in two kinds of kaolin clays
No.
Location
Sample
Note
Ka-ML
Ka-JX
Ka-MC
Ka-DYG
Hunan Miluo
Henan Jiaxian
Henan Mianchi
Henan Dayugou
Soft kaolin
Hard kaolin
Hard kaolin
Hard kaolin
1.00
0.77
0.82
0.74
Weather-eluviation type
In coal-bearing strata
In bauxite horizon
In coal-bearing strata
1282
Table 3
The compositions of the kaolin samples (wt%)
No.
Sample
SiO2
Al2 O3
MgO
CaO
TFe
TiO2
K2 O
Na2 O
Ka-ML
Ka-JX
Ka-MC
Ka-DYG
Soft kaolin
Hard kaolin
Hard kaolin
Hard kaolin
44.73
44.22
41.41
47.03
38.16
37.66
38.35
37.20
0.023
0.093
0.33
0.071
0.059
0.074
0.098
0.110
0.11
0.54
0.39
0.67
0.05
0.22
1.68
0.69
0.15
0.064
0.83
1.03
0.056
0.049
0.094
0.2
-16
3.8
-18
Zeta Potential (mV)
3.6
iep
3.4
3.2
3.0
iep=10.94 - 0.17SiO2 )
R=-0.93,SD=0.19,N=4
2.8
42
(a)
43
44
45
SiO2 (%)
46
-24
-26
-28
47
37.2
3.8
-16
3.6
-18
3.4
3.2
iep=-20.42 + 0.63 Al 2O3
R=0.77,SD=0.33,N=4
3.0
37.4
(a)
iep
-22
-30
41
2.8
38.2
38.4
Zeta=-13.85 - 24.57 T Fe
R=-0.99,SD=0.78,N=4
-20
-22
-24
-26
-28
-30
37.2
(b)
Zeta=-354.41 + 8.72 Al 2 O 3
R=0.76,SD=4.74,N=4
-20
37.4
37.6
37.8
38.0
38.2
38.4
Al2O 3 (%)
0.1
0.2
0.3
(b)
0.4
0.5
0.6
0.7
T Fe (%)
Fig. 4. Plots of the zeta potential (pH 7.3) vs. chemical composition
(oxides wt%) of the dierent kaolins: (a) the oxides wt% of Al2 O3 and
(b) the oxides wt% of TFe.
3.6
80
Recovery (%)
3.8
iep
3.4
3.2
iep=2.88 + 0.62 HI
R=0.17,SD=0.51,N=4
3.0
1283
70
60
soft kaolin
hard kaolin
50
40
2.8
2
0.70
0.75
0.80
0.85
0.90
0.95
6
pH
1.00
Fig. 5. Plots of the crystallinity index (HI) of kaolinites vs. the surface
iso-electric points (IEP) of the dierent kaolins.
10
12
Fig. 8. Flotation recovery of the dierent kaolin vs. pH with a collector of cetyl trimethyl ammonium bromide (2 104 M).
100
-16
90
Recovery (%)
-18
-20
-22
-24
70
soft kaolin
hard kaolin
60
-26
Zeta= - 66.29 + 50.38 HI
R=0.99,SD=1.19,N=4
-28
50
0
-30
0.70
0.75
0.95
1.00
Fig. 6. Plots of the crystallinity index (HI) of kaolinites vs. the zeta
potential (pH 7.3) of the dierent kaolin.
100
90
Recovery (%)
80
80
70
60
soft kaolin
hard kaolin
50
2
6
pH
10
12
Fig. 7. Flotation recovery of the dierent kaolin vs. pH with a collector of dodecyl amine acetate (2 104 M).
lower for hard kaolin than for soft kaolin, such that the
oatability of hard kaolin was lower than that of soft
kaolin. Weaver and Pollard (1983) submitted that
poorly ordered hard kaolins associated face surfaces of
kaolinite to face surfaces of kaolinite (FF) occulation in sea-water, whereas well ordered soft kaolins
maybe associated edge surfaces of kaolinite to face
surfaces (EF) occulation in freshwater. The soft
kaolin had more pore space than the hard kaolin. The
rock hardness of the hard kaolin was high. The major
textures of the hard kaolin clay were detrital texture,
cryptocrystalline texture and uxion texture etc. The
essential mineral kaolinite approximately directionally
arrayed in the hard kaolin clay. After the hard kaolin
clay had been ground, the particles, which consisted of
FF kaolinites, would occulate in the solution. The
particles of hard kaolin would disperse at the approximate point (pH 7.3) of zero net proton charge of
edge surface of the kaolinites. The well ordered soft
kaolin loosely aggregated. The essential mineral kaolinite may form the soft kaolin clay in edge surfaces to
face surfaces (EF) of kaolinite. The soft kaolin particles were prone to dispersal in the solution and to reaction with the agents. Therefore, the oatability of soft
kaolin is higher than that of hard kaolin.
1284
4. Conclusion
The surface zeta potential variation of the hard kaolins as a function of pH was almost the same as that of
the soft kaolin. The IEP of the hard kaolins varied from
2.5 to 3.8. SiO2 (wt%) of the several kaolins showed
negative correlation with IEP, but Al2 O3 (wt%) showed
positive correlation with IEP. The crystallinity index of
kaolinites was not the major factor determining IEP. In
the broad range of pH, the negative potential of the hard
kaolin was lower than that of the soft kaolin. At the
point (pH 7.3) of zero net proton charge of edge of
the kaolinite, TFe (wt%) showed negative correlation
with surface zeta potential of the kaolin, but the crystallinity index of kaolinite showed positive correlation.
The mineralsolution interface reaction played a pivotal
role in determining the surface zeta potentials of the
kaolins. More work is needed to fully understand the
surface properties and oatabilities of kaolins.
Acknowledgements
The authors would like to thank the Chinas Important Basic Research Program (G1999064901) and
National Fund for Distinguished Young Scholar
(59925412) for the nancial support of this research.
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